JPS6020902A - Production of microgel dispersion - Google Patents

Abstract

PURPOSE:To facilitate the production of a stable microgel dispersion, by reacting a nonaqueous dispersion of a functional group-containing vinyl polymer with a vinyl monomer reactive with the functional group to introduce unsaturated groups into the polymer and polymerizing the unsaturated group-containing polymer. CONSTITUTION:A vinyl monomer (e.g., hydroxyethyl acrylate) is polymerized in an organic liquid which can dissolve the monomer but can not dissolve a vinyl polymer formed therefrom (e.g., hexane) in the presence of a dispersion stabilizer soluble in the organic liquid to form a nonaqueous dispersion in which the dispersion stabilizer and/or the vinyl polymer have functional groups (e.g., hydroxyl group). A vinyl monomer which can be added to or condensed with the functional groups (e.g., glycidyl acrylate) is added and reacted with the polymer to introduce unsaturated groups thereinto, and the unsaturated group-containing dispersed phases are polymerized to obtain the purpose microgel dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a microglue dispersion, and more specifically, to a method for producing a microglue dispersion, and more specifically, a method for producing a stable microglue dispersion obtained by polymerizing a hindlimb dispersion containing a polymerizable unsaturated group. This relates to a manufacturing method.

Conventionally, microglue dispersion liquids have been produced by emulsion polymerization method or non-aqueous dilution method, but according to the method, the reaction is carried out with a solid content of 8 to 8%.
If the concentration is as low as 16%, the reaction progresses too much, and the polymerization conditions for creating microgels are insufficient, the microgels will react with each other to form secondary particles and become coarse particles. It is difficult to control the reaction process. On the other hand, according to the valve water dispersion method, the reaction can be carried out at a high concentration of 50-60% solids, but in order to improve the stability of the dispersion, particles may be crosslinked or particles may be grafted with a stabilizer. method is being used. However, the result is not enough.
()・Not done.

Note that the microgel dispersion in the present invention refers to one in which polymer particles having a particle size equivalent to that of conventional non-aqueous resin dispersions and having high crosslinkability are dispersed in an organic liquid.

We have discovered that by using a system unsaturated resin dispersion (such as JP-A-51-55344), it is possible to provide a microgel dispersion with a high solid content, easy control of the reaction process, and good dispersion stability. The present invention has been completed.

That is, the present invention provides (4) dissolving the vinyl in an organic liquid that dissolves the vinyl monomer but not the vinyl polymer formed from the monomer in the presence of a dispersion stabilizer that is soluble in the organic liquid. A dispersion obtained by polymerizing monomers, in which the dispersion stabilizer and /4fc are a step of producing a non-aqueous dispersion in which the vinyl polymer has a functional group; The process of reacting vinyl monomers with synthetic reactivity to produce a non-aqueous dispersion liquid with 97 unsaturated groups: The present invention relates to a method for producing a microgel dispersion comprising: polymerizing a group-containing dispersion.

The non-aqueous dispersion obtained in step (5) in the present invention is
A vinyl monomer that dissolves in the dispersion medium (organic liquid mainly composed of aliphatic hydrocarbons) with the dispersion stabilizer in combination with the stabilizer, but whose polymer does not dissolve in the dispersion medium. It is obtained by polymerizing.

As a dispersion medium, aliphatic hydrocarbons, ie, general.

Mainly petroleum fractions are used, such as pentane, xane, heptane, octane, minerals such as subiris 1-, and nappe. Dispersion stabilizers are located on the surface of polymer particles and form a stabilizing layer to maintain the dispersed state of the particles.

Stabilizing resins such as hydrocarbon polymers such as decomposed natural rubber, polybutadiene, and polyisoprene;
There are acrylic polymers, polyesters, alkyl polymers, cellulose derivatives, etc., and there are also acrylic polymers, polyesters, and cellulose derivatives.
Examples include block or graft polymers.

The vinyl polymer that becomes the main dispersed particles is, for example, a polymer or copolymer such as styrene, an acrylic monomer, a methacrylic monomer, or vinyl acetate.

Introduction of functional groups into dispersion stabilizers and/or vinyl polymers The functional groups to be introduced include a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, a certain mimethylol group, an alkoxymethylol group, an isocyanate group, an amide group, an amino group, and a chloro group. One or more of these functional groups can be introduced.However, when two or more functional groups are used simultaneously as the dispersion stabilizer and/or the functional group introduced into the vinyl polymer, if the functional groups are mutually Combinations that easily react at room temperature and in a short time must be avoided.These combinations include: hydroxyl group, carboxylic acid anhydride, hydroxyl group, incyanate group, methylol group, incyanate group, epoxy group, carboxyl group, epoxy group, and amine. Combinations such as a carboxylic acid anhydride group, an amino group, an amino group, a chloro group, a hydroxyl group, a chloro group, an epoxy group, a chloro group, an epoxy group, and a carboxylic acid anhydride group are possible.

When introducing a functional group into a dispersion stabilizer, the dispersion stabilizer or an acrylic polymer must be copolymerized with a vinyl monomer having a functional group, such as those shown in Table 1. Bye. Other copolymerized vinyl monomers, styrene, a-methylstyrene, vinyltoluene, acrylic esters (methyl, ethyl, butyl, 2-ethylhexyl, octyl, cyclohexyl ester)
, meccrylic acid ester (methyl, ethyl, butyl, 2
- Ethylhexyl, lacryl, stearyl ester, etc.), acrylonitrile, methacrylic V nitrile, vinyl acetate, and long chain esters of acrylic acid or methacrylic acid (those having an alkyl group, polyester group, etc. with a molecular weight of 300 to 3000 in the side chain), etc. be.

Table 1 Note: When the dispersion stabilizer is an alkyd resin or a polyester, since it is produced by a reaction between an acid and an alcohol, a hydroxyl group and/or a carboxyl group can remain in the resin skeleton. When the acid fraction stabilizer is an acrylic graft polyester, the methods for introducing the acrylic polymer and the methods for introducing the polyester can be used in combination.

When the dispersion stabilizer is a cellulose derivative, it naturally has a hydroxyl group.

In addition, when the dispersion stabilizer is decomposed natural rubber or polybutadiene, hydroxyl groups and
Carboxyl groups, carboxylic acid anhydrides, epoxy groups, etc. can be introduced. In addition, any dispersion stabilizer that is effective as a dispersion stabilizer and has the skeletal group mentioned above in the present invention can be used as an example of a dispersion stabilizer having a functional group.

The molecular weight of these dispersion stabilizers is 1.0 in number average molecular weight.
A range of 00 to 200,000 is preferred. molecular weight is 1,
If it is less than 000, the ability as a dispersion stabilizer is lost and a stable dispersion cannot be obtained. Also, 200.000
If it is larger, the viscosity of the dispersion becomes high, making it difficult to achieve high solid content and low viscosity, which is one of the characteristics of the wood invention.

The amount of functional groups in the dispersion stabilizer is determined by the molecular weight of the dispersion stabilizer: 1.
0.5 to 7.0 pieces per 000 units is preferable, and 0.5
If the number is less than 7,0, polymerizable unsaturated groups will be introduced, resulting in poor dispersion stability after microgel formation.If there are more than 7,0, the polar effect due to functional groups will increase and the ability as a dispersion stabilizer will decrease. It is not possible to produce a stable dispersion.

On the other hand, when introducing a functional group into a vinyl polymer, it can be easily introduced by using the vinyl monomers shown in Table 1 in the step of producing a dispersion. In this case, the amount of functional groups is 0.5 per 1.000 units of molecular weight of the vinyl polymer.
~7.0 is preferable; if it is less than 0.5, polymerizable unsaturated groups will be introduced, resulting in microgelation, resulting in poor dispersion stability, and if it is more than 7.0, it will have a negative effect on coating performance. give. The molecular weight of the vinyl polymer is not particularly limited, but the number average molecular weight is usually within a common sense range of 2.000 to 1.00.
If it is less than 0,000 and 2,000, it tends to cause physical and chemical deterioration of the coating film performance. If it is larger than J, OOO, 000, the fusion of dispersed particles will be hindered and problems will arise in film forming properties.

As other copolymerizable vinyl monomers, those exemplified as copolymerizable vinyl monomers in the above-mentioned dispersion stabilizer can be used.

In this way, a non-aqueous dispersion having a functional group in either or both of the dispersion stabilizer and the vinyl polymer can be obtained.

Of course, depending on the dispersion state, the dispersion liquid may contain polymers mainly consisting of particles, microparticles, free dispersion stabilizers, non-particulate vinyl polymers, etc. (hereinafter these may also be collectively referred to as dispersions). ) exists.

Subsequently, in the wood invention process, a polymerizable unsaturated group is introduced by reacting the functional group in this dispersion with a polymerizable vinyl monomer having a group capable of addition or condensation reactivity with the functional group. do. Table 2 shows the combinations of this introduction method.

The second surface may be reacted with 0.1 mole or more per mole of functional groups in the dispersion, and two or more types of vinyl monomers can be used in combination. Moreover, even if more than 1 mol is used, there is no problem because these vinyl monomers act as a crosslinking agent during curing. During the reaction, if necessary, a known catalyst having a reaction promoting effect can be used.

For example, in addition reactions between hydroxyl groups and incyanate groups, there are soot compounds such as stannous chloride and methyltin dichloride, amine compounds such as N-methylmorpholine, zinc compounds, iron compounds, and carboxyl groups. In addition to tertiary amines such as triethylamine, acidic catalysts and quaternary ammonium salts can be used in the addition reaction between and epoxy groups. In the dehydration reaction with carboxyl groups and hydroxyl groups, acidic catalysts such as sulfuric acid and known esterification catalysts such as digtyltin oxide can be used.

Water acts as a catalyst between carboxylic acid anhydride groups and epoxy groups, and acidic catalysts such as hydrochloric acid, phosphoric acid, oxalic acid, and p-toluenesulfonic acid are used in the ether exchange reactions between methylol groups and hydroxyl groups, and between methylol groups and alkoxymethylol groups. , alkaline catalysts such as potassium hydroxide, aqueous ammonia, and amine catalysts such as triethylamine and digtylamine can be used. Known catalysts can be used in other reactions as well.

Here, we will provide an overview of the manufacturing process to date.

The dispersion stabilizer can be obtained by a known polymerization method, condensation method, or addition reaction method. To create a stable dispersion, place an organic liquid (dispersion medium) mainly composed of aliphatic hydrocarbons and a dispersion stabilizer in a reaction vessel, heat it to 60 to 140°C, and then add vinyl monomer (dispersion stabilizer). (sometimes mixed with vinyl monomer) and a polymerization catalyst is added dropwise over a period of 1 to 7 hours. It is obtained by continuing the reaction for 2 to 7 hours. Here, the amount of the dispersion stabilizer is 0.5 to 70% by weight based on the total amount of the vinyl monomer and the dispersion stabilizer. If it is less than 0.5% by weight, a stable dispersion cannot be produced. If the amount exceeds 70% by weight, the dispersion system becomes a solution and loses its characteristics (high solid content, low viscosity). The concentration of the vinyl monomer and the dispersion stabilizer in the shattered dispersion is usually 30
~70% by weight. After the dispersion is prepared, a polymerizable vinyl monomer having reactivity for addition or bonding is subsequently introduced into the dispersion in its entirety or by a dropwise addition method to carry out a reaction. The reaction temperature varies depending on the reaction type, but is usually 60 to 160°C. In this case, care must be taken in advance to select a dispersion medium having a boiling point so as not to hinder the temperature rise during the subsequent addition or condensation reaction during the production of the dispersion. The addition or condensation reaction can be monitored by monitoring the acid value, incyanate value, hydroxyl value, epoxy value, amount of reaction-eliminated fraction, etc., depending on the reaction type. Further, during this addition reaction, if necessary, a known polymerization inhibitor may be added in order to prevent polymerization of the addition- or condensation-reactive polymerizable vinyl monomer.

In this way, polymerizable unsaturated double bonds can be introduced into the dispersion in the dispersion.

Next, a microgel dispersion is produced by polymerizing part or all of the unsaturated group-containing dispersion in the unsaturated group-introduced non-aqueous fraction obtained in the step (O).

The microgel dispersion can be produced by adding a suitable (1) thermal decomposition catalyst to the dispersion, (2) adding a catalyst for room temperature decomposition, or polymerizing the dispersion (3) in an inert gas. There is a method of heating and polymerizing. .

In the present invention, it is possible to manufacture by using these manufacturing methods (1) to (3) alone, and it is also possible to manufacture by combining (1) to (3) arbitrarily. The amount of the catalyst used is usually in the range of 01 to 10% by weight based on the resin content in the nonaqueous dispersion into which unsaturated groups have been introduced.

When using a thermal decomposition catalyst, the decomposition catalyst is added to the dispersion at room temperature, and the dispersion is gradually heated to the boiling point of the dispersion medium in the dispersion, and the polymerization reaction is carried out at the boiling point temperature for several hours to several tens of hours. ,
The dispersion liquid is heated to the boiling point of the dispersion medium, a hindlimb decomposition catalyst is added, and a polymerization reaction is carried out at the boiling point temperature of the dispersion medium for several hours to several tens of hours.

Examples of thermal decomposition catalysts include benzoyl peroxide, butyl perbenzoate, diteryl peroxide,
Examples include Y. Liebder's peroxide, cumene hydroveroxide, methyl ethyl lactone peroxide, azobisisobutyronitrile, and azobisdimethylvaleronitrile.

When using a room temperature decomposition catalyst, the dispersion catalyst is added to the dispersion liquid, polymerization reaction is carried out at room temperature for several hours to several tens of hours, and then the dispersion liquid is polymerized for four to several tens of hours at the boiling point of the dispersion medium in the dispersion liquid. Make it react.

Examples of the room temperature decomposition catalyst include redox catalysts such as benzoyl peroxide-triethylamine type and methyl ethyl ketone peroxide cobalt naphthenate yarn.

When polymerizing a dispersion liquid in an inert gas, the dispersion liquid is gradually heated to the boiling point temperature of the dispersion medium in the dispersion liquid, and an inert gas is blown onto or into the liquid. The polymerization reaction is carried out for several hours to several tens of hours.

Examples of the inert gas include nitrogen gas, carbon dioxide gas, helicum gas, neon gas, argon gas, radon gas, and krypton gas.

The microglue dispersion thus obtained can be used for applications such as paints, molded products, adhesives, etc. by means of thermal polymerization curing, photopolymerization curing, electron beam polymerization curing, catalytic polymerization curing, etc.

The microglue dispersion of the present invention can be used as is, but some or all of the organic liquid (dispersion medium) may be added to the dispersion.
It is also possible to substitute with a vinyl monomer or two or more types of vinyl monomers, and it can also be mixed with saturated resins that do not have polymerizable unsaturated groups and unsaturated resins that have polymerizable unsaturated groups. Stabilizers, colorants, plasticizers, etc. can also be mixed in, if necessary.

Examples of vinyl monomers to be substituted include styrene, α-methylstyrene, vinyltoluene, acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, acrylamide, and vinyl acetate. As a polyvinyl compound, the molecular weight is 1. (2 below 100
Compounds having ~4 polymerizable vinyl groups, such as diallyl 7-crate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bis-(ethylene glycol 7-thalerate) di(meth)acrylate, bis- -(diethylene glycol di(meth)acrylate), polyethylene glycol di(meth)acrylate, polyglobylene glycol di(meth)arylate, trimethylolpropane)-(meth)acrylate, Examples include an adduct of diisocyanate and hydroxyalkylnisder (meth)acrylate (1:1 (mole ratio)) and an addition reaction product of trimethylolecne or trimethylolpropane, pentaerythritol tetra(meth)acrylate, and the like.

Saturated resins without polymerizable unsaturated groups include vinyl resins, acrylic resins, alkyd resins, flexible resins, epoxy resins, and the like.

Examples of unsaturated resins having a polymerizable unsaturated group include unsaturated polyester resins, polynisder (meth)acrylate resins, polycretane (meth)acrylate jugeji, epoxy (meth)acrylate resins, polyol (meth)acrylate resins, and polyethers. There are (meth)acrylate resins, etc.

Colorants include dyes, organic pigments, and inorganic pigments.

Plasticizers tend to be low molecular weight plasticizers such as dimethyl tuclate and dioctyl tuclate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers, and can also be used by mixing them into the microgel dispersion. When producing a microgel dispersion, it is dissolved in vinyl monomer, and then dissolved in the dispersed particles of the produced dispersion (mainly in the polymer particles).
It can also be distributed to

A photosensitizer is used when the microgel dispersion of the present invention is subjected to a photopolymerization curing reaction. The amount of photosensitizer is suitably in the range of 0.01 to 10% by weight based on the total amount of resin.

Examples of photosensitizers include benzoin, benzyl, benzin alkyl ether (alkyl group CnH2n-Hn
= 1-18) and other benzoin compounds, 2.2
'-Azobisisobutyronitrile, 2-phenylazo2
．． Aso-based compounds such as 4-dimethyl-4-methoxyvaleronitrile, 2-phenyl'y-so-2,4-dimethylvaleronitrile, and iodine-based compounds such as diphenyl disulfide, tetramethylthiuram monosulfide, and ide. In addition, benzophenone, anthraquinone,
When subjecting to 5-dinitro catalytic polymerization hardening, a suitable thermal decomposition catalyst and room temperature decomposition catalyst are used. The amount of catalyst used is usually in the range of 0.01 to 10% by weight based on the total amount of resin.

Examples of thermal decomposition catalysts include benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, and azobisdimethylvaleronitrile.

Examples of room temperature decomposition catalysts include redox catalysts such as benzoyl peroxide-triethylamine type and methyl ethyl ketone peroxide-cobalt naphthenate type catalysts.

It is permissible to add an organic solvent to the dispersion of the present invention, that is, a solvent used as a thinner thinner and film coalescing agent for adjusting viscosity.

Zero-shot F! According to AK, a polymerizable unsaturated double bond is introduced into a dispersion and a free dispersion stabilizer in a dispersion liquid generally referred to as a non-aqueous dispersion, and a part of the polymerizable unsaturated double bond is Alternatively, all of the particles are polymerized, and a microgel dispersion with good dispersibility can be obtained by microgelation of the dispersion and grafting of the particles and the dispersion stabilizer.

Next, the present invention will be explained by examples. parts, %, weight parts, weight %.

Example 1 1) Production of IP-aqueous dispersion The following substances were added to a flask and stirred while heating to 90 to 100° C. while blowing nitrogen gas to dissolve well.

EAB551-02 20 parts (trade name of Eastman Chemical Company) Butyl acetate 100 Aliphatic hydrocarbons (B, P, 120-140°C) 00 The following substances were then added and reacted at 100°C for 30 minutes. .

t-butyl peroctoate 20 parts Methyl methacrylate 50 parts After that, add one drop of the following mixture to the hole every 3 hours.

Methyl methacrylate 300 parts 2-hydroxyethyl acrylate 90 Plug acrylate 40 t-butyl peroctoate 10 Aliphatic hydrocarbons (B, P, 120-140°C) 100
After aging for 2 hours, a white viscous dispersion was obtained, and when 100 parts of aliphatic hydrocarbon was added with further stirring, a stable dispersion was obtained. The non-volatile content is 50%.

l) Production of non-aqueous dispersion with unsaturated groups introduced The following substances were added to the above dispersion and reacted at 80° C. for 4 hours to introduce unsaturated groups.

1=1 (molar ratio) addition reaction product of tolylene diisocyanate and 2-hydroxyethyl acrylate 300 parts Hydroquinone 0.5 Butyl acetate 100 Aliphatic hydrocarbon (B, P, 120-140°C) 200
The reaction was monitored by NC0 value, and a value of 1 or less was considered the end point.

■) Microglu dispersion! 1! A more stable microglue dispersion was obtained by heating and stirring the above-mentioned dispersion while passing nitrogen gas through it and reacting for 6 hours at the boiling point of the dispersion medium.

Example 2 5 parts of azobisisobutyronitrile was added to 100 parts of the unsaturated group-introduced nonaqueous dispersion obtained in the same manner as in Example 1, and the temperature was raised by changing the boiling point of the dispersion medium while stirring. , and then further reacted at boiling point for 3 hours.

The microgel dispersion thus obtained is Example 1
It was also stable.

Example 3 (1) Preparation of non-aqueous dispersion The following substances were placed in a flask, heated and stirred while blowing nitrogen gas, and the temperature was raised to 90-100°C.

Mineral spirit 1,000 parts Nl5SO-FB (B-3000), 500 (trade name of Nippon Soda Co., Ltd. product) Next, the following mixed solution was added dropwise over 3 hours, and then aged for 2 hours.

Acrylonitrile 170 parts Methyl methacrylate 150 parts 2-hydroxyethyl acrylate 60 parts Azobisisoprodylonitrile 10 The milky white stable dispersion thus obtained has a non-volatile content of 5 parts.
It was 0%.

I) Preparation of non-aqueous dispersion with unsaturated groups introduced The following substances were added to the above dispersion, reacted at the reflux temperature of mineral spirits, and unsaturated groups were introduced by ether exchange.

N-methylol acrylamide 52 parts P-toluenesulfonic acid 0.5 8.52 parts of water came out in about 5 hours. Next, track the reaction by the amount of water flowing out.

厘) Production of microgel dispersion A stable microgel dispersion was obtained by adding 0.5 part of t-butyl peroctoate to the above-mentioned unsaturated group-introduced dispersion and reacting for 3 hours at the reflux temperature of mineral spirit. Ta.

Example 4 ■) Production of dispersion stabilizer (3) The following substances were placed in a flask and heated to reflux temperature, and a binding reaction was carried out until the acid value ( ) became 5 or less.

Pentaerythritol 816 parts Adipic acid 730 Toluene 15 Furthermore, 2520 parts of tall oil fatty acid were added, and the condensation reaction was carried out at the reflux temperature as before at an acid value (1.5 or less).

Next, 740 parts of phthalic anhydride, boiling point range 120-140
4,464 parts of an aliphatic hydrocarbon at 80° C. were added thereto, heated to 80° C., and reacted until the acid value reached 48.3. Do not heat above 80°C at this stage. The condensate thus obtained had a nonvolatile content of 50%.

Production of non-aqueous dispersion (9) Next, place the following substances in a flask, heat to 90°C, and stir.

Combined product obtained in (a) 200 parts Normal hebutane 30 Butyl acetate 13 Methyl acrylate 9.6 Styrene 10.0 Acrylonitrile 5.1 2-hydroxyethyl acrylate 11.2 Acrylic acid 7.1 Azobisisobutyro A 1.5 nitrile mixture was added dropwise into the flask over a period of 3 hours,
The reaction was continued for an additional 2 hours. The polymer solution thus obtained was milky white and had a nonvolatile content of 50%.

I) Production of unsaturated group-introduced non-aqueous dispersion Add the following substances to 200 parts of the above dispersion, and add the following substances to 90°C 8
Allowed time to react.

Glycidyl methacrylate 57 parts Triethylamine 0.3 Hydroquinone 0.1 The reaction was monitored by acid value, and a value of 1 or less was considered the end point.

■) Production of microgel dispersion The above-mentioned unsaturated group-introduced dispersion (azobis isoptiloni)
A stable microgel dispersion was obtained by adding 0.5 part of IJ and reacting for 3 hours at reflux temperature while blowing nitrogen into the solution at a flow rate of 0.3 t/-.

Example 5 I) Production of dispersion stabilizer The following substances were placed in a flask, heated to 110°C, and stirred.

Acetic acid butyl ester 15 parts Aliphatic hydrocarbon having a boiling point range of 120 to 140°C 84.4 Then, the following mixture was added dropwise over 3 hours, and
A time reaction was performed.

2-ethylhexyl acrylate 73.6 parts 2-hydroxyethyl acrylate 11.6 azobisisobutyronitrile 1.0 The obtained polymerization solution had a nonvolatile content of 50%.

I) Production of nonaqueous dispersion (B) The following substances were placed in a flask, heated to 90°C, and stirred.

Solution obtained in (2) 120 parts aliphatic hydrocarbon having a boiling temperature of 120 to 140° C. 140 Then, the following mixture was added dropwise to the flask over 3 hours, and the reaction was further carried out for 2 hours.

Styrene 23.3 parts Acrylonitrile 21.7 2-Hydroxyethyl acrylate 95.0 Benzoyl peroxide 2.1 The polymer solution thus obtained was milky white and had a non-volatile content of 50%.
The emulsion had good storage stability.

Summer) Production of non-aqueous dispersion with unsaturated groups added To 200 parts of the dispersion described in section Y, add the following compound.
The reaction was carried out at 20°C for 10 hours.

Acrylic acid 2.2 parts Triethylamine 0.01 Then, 44 parts of maleic anhydride was added to 120 parts.
The reaction was carried out for 3 hours at °C, and the total acid value and half acid value were measured, and the end point was defined as the point where 95% or more of the acid anhydride groups had reacted. Next, 64 parts of glycidyl acrylate was added and reacted at 120°C for 10 hours.

ff) Production of E clogel dispersion To 100 parts of the above unsaturated group-introduced dispersion, 0.5 part of tertiary-butylperbenzony) was added, and 5
Allowed time to react. The resulting microglue dispersion was stable.

Claims (1)

[Claims] 1. (A) Presence of a dispersion stabilizer soluble in the organic liquid in an organic liquid that dissolves the vinyl monomer but does not dissolve the vinyl polymer formed from the monomer. 1. A step of producing a non-aqueous dispersion in which the dispersion stabilizer and/or the vinyl polymer has a functional group (B) a step of reacting the aqueous dispersion with the functional group and a vinyl monomer having addition and condensation reactivity to produce an unsaturated group-introduced non-aqueous dispersion;
and (0) a step of polymerizing an unsaturated group-containing dispersion in the unsaturated group-introduced non-aqueous dispersion; 2. The functional group is a hydroxyl group, a carboxyl group, a carboxylic acid anhydride. 2. The method for producing a microgel according to claim 1, wherein the functional group is at least one kind of functional group selected from a group consisting of a group consisting of a group consisting of epoxy group, an epoxy group, a methylol group, an alkoxymethylol group, an isocyanate group, an amide group, an amino group, and a chloro group.